Chemical compounds and processes



Patented Sept. 24, 1946 UNITED STATES PATENT OFFICE 2,408,232 CHEMICAL CODIPOUNDS AND. PROCESSES Herschel G. Smith, Wallingford, and Troy L. Cantrell, Lansdowne, Pa., assignors to Gulf Oil Corporation, Pittsburgh, Pa.,' .a corporation of Pennsylvania No Drawing. Application January 7; 1946, Serial N0. 639,701

Claims. (Cl. 260-461) This invention relates to new chemical com- It is insoluble in water and soluble in mineral oils pounds and processes and more particularly to to the extent of 11.70 parts in 100 parts of oil at new aromatic amine salts of 3-methyl-butyl, 2- 20 C. It has the structural formula: ethyl-hexyl orthophosphate which are useful for fl H various technical purposes especially in the petroleum industry. 5 HTO (|JT$ OTI O (IJ OH This application is a continuation-in-part of Hi0 H H H E 02115 our copending appli ation, e ial ,4 fi The following examples illustrate but do not August 3, 1942, which application is in turn a limitiourinvehtion continuation-in-part of our application, Serial No.

421,842, filed December 5, 1941. Application Serial 7 Example I No. 453,458 became U. S. Patent No. 2,397,377 on One hundred and twenty-one pounds of di- March 26,1946. methylam'line were added to an iron vessel This invention has as an object the production equipped with an air lance and 281 pounds of 3- of new chemical compounds that are technically 5 methyl-butyl, 2-ethyl-hexyl orthophosphate were useful. A further object is to prepare these new introduced over a period of one hour; the slow compounds by novel and easily conducted procrate of addition being desirable to maintain the esses. A still further object is to utilize these temperature of the reaction mixture below 185 F. new compounds for various technical purposes. At the conclusion of this reaction, the tempera- Other objects will appearhereinafter. ture was 180 F., and the pH of the mixture was These objects are accomplished in accordance 2.0. A pH of 3.0 was desired; 12.0 pounds of diwith the present invention by making aromatic methylaniline were added, which brought the pH aminesalts of 3-methyl-butyl, 2-ethyl-hexyl orto 3.0. The reaction product was an oily subthophosphate. Salts having the following forstance, readily soluble in mineral oils and having niula: h the following properties:

fi f 1 Gravity: A.P.I 7.4 11-c-o-o-o-r-o-C-o-H Specific gravity, 60/60 F 1.019 5 i 1 5 (132m I V1scos1ty,S.U.V.100 F 468 R 'IlI/R 7, Pour: F 1 -50 The reactionv product described above has the structural formula: V

H i i i i i ii j i*i V 35 i H H H H H CH wherein R represents a substituentselected from a [/H a 5 the class consisting of methyl and ethyl groups 7 O and hydrogen, are the preferred products of the I g present invention. I 0 3 CH3 In preparing these new salts, the selected aro- 40 As the dimethylaniline isoamyl octyl phosphate matic amine is reacted with B-methyl-butyl, 2- is substantially insoluble in water, the pH equivaethyl-hexyl orthophosphate to obtain :the desired lent is measured by the following expedient. Noraromatic amine salt thereof; the pH of the reacmal butanol (which contains a'small amount of tion mixture being adjusted to within the range water) is adjusted to exact neutrality, pH=7.0 2.0 to 5.5 in so preparing and recovering the and the sample is dissolved therein. The pH of amine salt. For example, dimethyl-aniline is the solution is then measured in the ordinary way brought into reaction with S-methyl-butyl, 2- as for aqueous solutions, by electrometric or ethyl-hexyl orthophosphate, and the pH of the colorimetricmethod-s. The butanol appears to reaction mixture is adjusted to within the range serve as a blending agent, for dissolving the sam- 2 to 4. With the theoretical molecular ratio of ple in the water.

the two reactants, namely 1:1, the product is apt It will be noted that the measured pH of the to be slightly too acid, with a pH below 2, and this aminophosphate is low despite the fact that a is taken care of by using a slight excess of the slight excess of amine is present. This is because dimethylaniline so that the molecular ratio is bethe reaction involves neutralizing a rather strong tween 1:1 and 1:1.1. v 35 acid with a very Weak base; lsoamyl octyl orthophosphate, which is also Example H called 3-methyl-butyl, 2-ethyl-hexyl orthophos phate, is a brown, oily liquid; its specific gravity O e hund ed and forty-nine P ds of 01161711- is 1.009 at 24/4 C., and its viscosity is 210, 75 and ylaniline were added to an iron vessel equipped 29 centipoises at 25, 50 and 75 C. respectively. with an air lance, and 281 pounds of 3-methylbutyl, Z-ethyl-hexyl orthophosphate were introduced over a period of one hour; the slow rate of addition being desirable to maintain the temperature of the reaction mixture below 185 F. At the conclusion of this reaction, the temperature was 180 F. and the pH of the mixture was 2.0. A pH of 3.5 was desired; a further 15 pounds of diethylaniline were added, which brought the pH to 3.5. The reaction product was an oily liquid which was readily soluble in mineral oils.

The reaction product of diethylaniline with 3- methyl-butyl, Z-ethyl-hexyl orthophosphate has the following structural formula:

As the diethylaniline isoamyl octyl phosphate is substantially insoluble in water, the pH equivalent is measured by the expedient described above in Example I. Here again, the measured pH of the amino-phosphate is low despite the fact that a slight excess of amine is present.

Example III sired; a further 9 pounds of aniline were added,-

which brought the pH to 3.5. The reaction product was an oily liquid which was readily soluble in mineral oils.

The reaction product of aniline with 3-methylbutyl, Z-ethyl-hexyl orthophosphate has the following structural formula:

As the aniline isoamyl octyl phosphate is substantially insoluble in water, the pH equivalent is measured by the following expedient. Normal butanol (which contains .a small amount of water) is adjusted to exact neutrality, pI-I='7.0, and the sample is dissolved therein. The pH of the solution is then measured in the ordinary way as for aqueous solutions, by electrometric or colorimetric methods. The butanol appears to serve as a blending agent for dissolving the sample in water.

It will be noted that the measured pH of this aminophosphate is low despite the fact that a slight excess of amine is present. This is because the reaction involves neutralizing a rather strong acid with a very weak base. Moreover, traces of mono-, diand tribasic acids may be formed under the conditions of the pI-I determination.

While aniline 3-methyl-butyl, Z-ethyl-hexyl phosphate is an effective foam suppressor for use in lubricating oils, it is more advantageous to employ the foam suppressors prepared from 3- methylbutyl, Z-ethyl-hexyl phosphate and dimethyl or diethyl aniline. This advantageous class of foam suppressors may be represented by the following formula:

wherein R represents a methyl or ethyl group.

While the preparation of the aniline, .dimethylaniline, and diethylaniline salts of S-methylbutyl, Z-ethyl-hexyl orthophosphate has been specifically described above, this invention is not so limited but pertains broadly to the preparation of any aromatic amine salt of S-methylbutyl, 2-ethyl-hexyl orthophosphate. Among the aromatic amines which may be used to prepare such salts there may be mentioned aniline, ortho-toluidine, meta-toluidine, para-toluidine, the various isomeric xylidines, the anisidines, the phenetidines, the nitroanilines, the chloroanilines, the aminophenols, the aminocresols, the phenylene diamines, the aminobiphenyls, alphanaphthylamine, beta-naphthylamine, N-methyl aniline, N-ethyl aniline, N-methyl beta-naphthylamine, diphenylamine, phenyl beta-naphthylamine, N-dimethyl aniline, N-diethyl aniline, N-dibutyl aniline, N-diamyl aniline, N-methyl diphenylamine, N-methyl phenyl beta-naphthylamine, N-dimethyl alpha-naphthylamine, etc.

While our invention has been described above with reference to various specific examples and embodiments, it will be understood that the invention is not limited to such illustrative examples and embodiments, but may be variously practiced within the scope of the claims herein made.

What we claim is:

1. An aromatic amine salt of 3-rnethyl-butyl, Z-ethyl-hexyl orthophosphate.

2. An aromatic amine salt of 3-methy1-buty1, 2-ethyl-hexyl orthophosphate having the formula:

i r i arr wre E30 H H O H H C H l/ R1TIR wherein R represents a substituent selected from the class consisting of methyl and ethyl groups and hydrogen.

3. The aniline salt of B-methyl-butyl, 2-ethy'lhexyl orthophosphate.

4. The dimethylaniline salt of '3-methylbutyl, Z-ethyl-hexyl orthophosphate.

5. The diethylaniline salt of B-methyl-butyl, 2- ethyl-hexyl ortho-phosphate.

HERSCHEL G. SMITH. TROY L. CANTRELL. 

